Stereoselective Rh-Catalyzed Hydrogenative Desymmetrization of Achiral Substituted 1,4-Dienes

Highly
efficient catalytic stereoselective hydrogenative desymmetrization
reactions mediated by rhodium complexes derived from enantiopure phosphine–phosphite
(P–OP) ligands are described. The highest performing ligand,
which contains a TADDOL-derived phosphite fragment [TADDOL = (2,2-dimethyl-1,3-dioxolane-4,5-diyl)­bis­(diphenylmethanol)],
presented excellent catalytic properties for the desymmetrization
of a set of achiral 1,4-dienes, providing access to the selective
formation of a variety of enantioenriched secondary and tertiary alcohols
(six examples, up to 92% ee).